CA1201835A - Process for the preparation of polymer dispersions - Google Patents
Process for the preparation of polymer dispersionsInfo
- Publication number
- CA1201835A CA1201835A CA000374396A CA374396A CA1201835A CA 1201835 A CA1201835 A CA 1201835A CA 000374396 A CA000374396 A CA 000374396A CA 374396 A CA374396 A CA 374396A CA 1201835 A CA1201835 A CA 1201835A
- Authority
- CA
- Canada
- Prior art keywords
- emulsifier
- oxyethylene units
- monomer
- process according
- polyoxyethylene chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
Abstract
ABSTRACT The invention concerns a process for the production of an aqueous polymer dispersion by emulsion polymerisation wherein at least one monomer containing a phosphoric acid, sulphonic acid or carboxylic acid group or emulsifying group is present , at least one emulsifier is present and in which at least one compound containing a polyoxyethylene chain of 60 to 400 oxyethylene units is present chosen from the group of polyoxyethylene glycols, emulsifiers containing a polyoxy-ethylene chain and copolymerisable monomers containing a polyoxyethylene chain. Said dispersion is very suitable for use in high-gloss paints.
Description
s The invention relates to a process for the preparation of aqueous dis-persions of a water-insoluble polymer, which can for ins-tance be used as paint binders. The invention relates in particular to dispersions -tha-t can be applied in combination with a polymer soluble in an aqueous alkaline medi.um.
I-t is known that an aqueous dispersion of a water-insoluble addition polymer, combined with a polymer tha-t is soluble in an aqueous ~lkal ~n~ environ-ment, can be applied as a binder for gloss paint. The coatlng ob-tained is formed substantially by -the insoluble polymer. The polymer that is soluble in an alkal-ine environment ensures good brushability of the system, in particular good flow behaviour, and a good gloss~ and is often used as a grinding aid for the pigment to be included in the paint. A disadvantage of the known systems, described in British Patent speciEication 1,500,517, among others, is that a relatively large quantity of the soluble polymer is required to obtain good brushability, in par-ticular flow. Owing to the presence of comparatively large quantities of alkali-soluble polymer, however, the coating becomes sensitive to moisture penetration, and the alkali resistance and the adhesion to the substrate deteriorate.
The purpose of the invention is an improved aqueous polymer dispersion, in particular a dispersion that can be applied as a binder for gloss paint.
According to one aspect of the present invention there is provided a process for preparing an aqueous dispersion of a water-insoluble polymer compris-ing effecting an addition polymerization of unsaturated monomers in water with an appropriate initiator and at least one emulsifier, wherein the polymeri7.ation mixture comprises between 0.1 and 5.0 wt. % calculated relative to the total quan-tity of monomer of at least one monomer containing a phosphoric acid, sulphonic acid or carboxylic acid group functioning as emulsifier, at least one anionic or non-ionic emulsifier in a quantity of between 0.1 and lO wt. %, calculated rela-tive to the total quantity of monomer, and at least one compound that contains a -33~;
polyoxyethylene chain having between 60 and 400 oxyethylene units and that is chosen from the group consisting oE polyethylene glycols, non-ionic emulsifiers,anionic emulsiEiers and copolymerizable oompounds.
According to another aspect of -the present invention there is provided an aqueous dispersion of a water-insoluble polymer prepared by -the above process.
According to a further aspect of the present invention -there is provi-ded a process for preparing an aqueous polymer dispersion with increased flow, wherein an aqueous dispersion oE a water-insoluble polymer containing between 0.1 and 5.0 wt. %, calculated relative to the total quantity of monomer, of a monomer possessing a phosphoric acid, sl1lphon;c acid or carboxylic acid group Eunctioning as emulsifier, in which dispersion there is at least one compound with a long polyoxyethylene chain containing between 60 and 400 oxyethylene units, chosen from the group of polyethylene glycols, non-copolymerizable non-ionic or anionicemlllq;fiers containing a polyoxye-thylene chain, and copolymerizable compounds containing a polyoxyethylene chain, is mixed with a polymer soluble in an aqueous alkaline medium in a vatio such that -there is between 1 and 25 wt. % alkali-solu-ble polymer present, calculated relative to the total quantity of polymer wherein the alkali-soluble polymer is a copolymer of an acrylate or methacrylate and an unsaturated mono- or dicarboxylic acid unit~
According to a still further aspect of the present invention there is provided a paint comprising a polymer dispersion having increased flow prepared by the above process as a binding agent.
According to another aspect of the present invention there is provided a polymerization mixture as defined above for use in the above process.
According to the invention, an aqueous dispersion of a water-insoluble polymer is prepared by addition polymerization of unsatura-ted monomers in waterwith an appropriate initiator and at least one emulsifier, at least one monomer la ~r~i b, ~
~2~ 335 containing a phosphoric acid, sulphonic acid or carboxylic acid group or a group acting as emulsifier being employed in a quantity of between 0.1 and 5.0 wt. %, calculatecl relative -to the to-tal quantity of monomers, and polymerization being conducted in the presence oE a-t least one non-ionic or anionic emulsifier in a quantity lb ~2~)183S
oi' between 0.1 and 10.0 wt.%, calculated relative to the total quantity oi' monomers, with at least one compound being presen-t that contains a polyoxyethylene chain containing between 60 and 400 oxyethylene units and that is chosen ~rom the group o~ polyethylene glycols, non-ionic or anionio non-copolymerizable emulsiiiers containing a poly-oxyethylene chain and non-lonic or anlonic copolymerizable emulsi~iers containing a polyoxyethylene oha~n.
The invention is based on the iact that at lsast one monomer built into the polymer contains a stabllizine acid group or an emulsi-~ying group and that there is at least one compound with a long poly-oxyethylene chain present. By this combination, dispersions can be obtained that posse3s long shel~ e and good dispersion ~low and good polymer water resistance. These dispersions can in general be applied in coating systems and paints, as additives in construction materials (plaster, cement and concrete mortars), as impregnating agents and adhesives.
The dispersions are especially suitable ~or applications in which a poly~er soluble in an aqueous alkaline environment is also added to the dispersion to improve the ~low. It is ~ound that only a minor quantity o~ alkali-soluble polymer is required to obtain 2 dispersion with good ~low properties. Such mixed systems can be used for the ai'orementioned applications. They are especially suitab}e i'or application as lacquers and as binding agents in gloss paints, more speci~ically air-drying gloss paint~.
The coatings thus obtained have a high gloss, adher~ well, are re-coatable and well resistant to water and alkali. The paints have good brushability due to their excellent i'low.
According to the invention, there should be at least one compound with a long polyoxyethylens chain pre~ent during poly~erization.
This chain should contain between 60 and 400 oxyethylene units. Hence-~orth, a polyoxyethylene group with n oxyethylene units will be indica-ted in complsx compounds by '.nE0', as ior instance in nonyl phenol-.100 E0. The value oi' n is the actual value, determined by analysis.
Polyethylene glycol with a molecular weight of between about 2600 and 15,000 and preferably between 3500 and 6000 can be used as compound with a long polyoxyethylene chain, in a quantity oi between 0.1 and 5.0 wt.%, calculated relative to the quantity o~ monomer. In `~ ~201835 addition to the polyethylene glycol, at least one anionic or non-ionic emulsi-fier should be used. In addition to the polyethylene glycol, an emulsifier with a long polyoxyethylene chain1 optionally copolymerizable, may also be ~Ised.
Application of polyethylene glycol gives good results, but has the disadvantage that an extra, water-soluble co~lponent is added in addition to the emulsifiers.
For this reason, a suitable non-ionic or anionic emulsifier is preferably used as compound with a long polyoxyethylene chain.
Non-ionic or anionic non-copolymerizable emulsifiers with a long poly-oxyethylene chain can be applied separately or in combination in a quantity of between 0.1 and 10 wt. %, preferably between 0.5 and 7.5 wt.%, and in particular between 1.0 and 5.0 wt.%, calculated relative to the quantity of monomer. The polyoxyethylene chain should contain between 60 and 400 oxyethylene units. The best results as regards the brushability, particularly the flow, of the disper-si~ons and lacquers and paints based thereon are achie~ed with chains containing 8Q to 120 oxyethylene units.
Non-ionic emulsifiers with a long polyoxyethylene chain that can potentially be used include a polyoxyethylated C6-C20 alcohol, a polyoxyethylated phenolformaldehyde condensa~e, a polyoxyethylated (C4-C20) alkyl phenol, a poly-oxyethylene-polyoxypropylene block copolymer, or an adduct of ethylene oxide and propylene oxide on a polyamine, which adduct contains one or more polyoxy-ethylene chains. The latter two types of emulsifier should consist to more than 60 wt.% and preferably at least 80 wt.% of polyoxyethylene chain(s). Ex-amples of suitable emulsifiers are nonyl phenol .80 E0, nonyl phenol .100 E0, .200 E0, nonyl phenol .12Q E0, stearyl .100 E0, n-butyl phenol .100 E0~ dodecyl phenol .150 E0, an ethylene oxide/propylene oxide ~80/20) block copolymer with a molecular weight of 8700, an adduct of ethylene oxide and propylene oxide on ethylene diamine consisting to 80 wt.% of oxyethylene units and with a molecular ~Z~ 3S
weight of 8000, and other commercially available products. The above-mentioned types of emulsifier are pre:ferably used in combtnation with a conventional anionlc emuls:ifier containing few or no oxyethylene groups, because polymerization can thus be better controlled.
In general, the sulphonated, phosphated and carboxylated analogues o-f the above-mentioned non-ionic emulsifiers are potential anionic emulsifiers with a long polyoxyctllylene chain, as such or in - 3a -lZ~D18a3S
the ~orm o~ alkali, ammonium or amine salts.
The carboxylate or phosphate product is pre~erablg used, due to the greater improvement o~ the flow behaviour. Examples o~
suitable oompounds are lauryl .l20 E0 phosphate, dodeoyl .100 E0 phos-phate, nonyl .150 E0 carboxylate, nonyl phenol .80 E0 sulphate, nonyl phenol .100 E0 carboxylate, hexyl phenol .120 E0 phosphate and analogou~
compounds.
In addition to the non-copolymerizable emulsiiiers with a long polyoxyethylene chain, other conventional non-ionic or anionic emulsi~iers may also be present that contain ~ew or no oxyethylene units. Examples o~ such non-ionic emulsi~ier3 include nonyl phenol ,20 E0, n-butyl phenol .40 E0, lauryl .25 E0 and ethylene oxide/pro-pylene o~ide block copolymers.
I~ there is a non-ionic 0mulsi~ier with a long polyoxy-ethylene chain present, it is of advantage to apply in addition ananionic emulsifier containing iew or no oxyethylene units. Examples o~ suitable anionic emulsi~iers o~ this type are di-(C6-C12 alkyl) sulphosu¢cinate, dodecyl sulphate, lauryl sulphate, (C4-C20 alkyl) benzene sulphonate, nonyl phenol .10 E0 sulphate, nonyl .5 E0 phosphate, lauryl ,lQ E0 carboxylate, stearyl .~ E0 phosphate and n-o~tyl phos-phate. The total quantity of non-copolymerizable emulsi~ier is 1n all cas0s between 0.1 and 10.0 wt.%, calculated relative to the quantity o~ monomer.
A copolymeri7.able emulsifier can also be used as compound with a long pclyoxyethylene chain, preierably in a quantity o~ between 1.0 and 5.0 wt.%, calculated relative to the total quantity of monomer.
Examples here are nonyl phenol .10~ E0 (hydroxyethyl methacrylate) phosphate, lauryl .120 E0 (hydroxyethyl methacrylate) phosphate, nonyl phenol .80 E0 2-sulphopropyl malea~e, a half-ester o~ maleic acid or ~umaric acid with an ethylene oxide/propylene oxide block copolymer (70 % E0, molecular weight 6500), lauryl .90 E0 2-sulphopropyl itacon-ate, butyl phenol .120 E0 methacrylate, and in general esters o~ a oopolymeri~able acidic compound with one of the non-ionic emulsi~iers with long polyoxyethylene chaine summed up above. These copolymsrizable emulsi~iers, too, should possess a group containing 60-~00 oxyethylene units, and preferably 80-120 oxyethylene units.
In addition to the oopolymerizable emulsiiiers, one or more 12l~ 5 non-copolymerizable emulsifiers can be used.
In the polymerization there should be present between 0.10 Qnd 5.~ wt.%, calculated relative to the total quantity of monomer, of a copolymerizable emulsifier and/Qr a copolymerizable emulsion stabi-lizer po~sesslng a sulphonic acid, phosphorio ac:ld or carboxylic acidgroup. Here, monomers are taken to mean any unsaturated copolymerizable oompounds present. Copolymerizable emulsifiers are known per se.
Examples are dodecyl-2-sulphopropyl itaconate, dodecyl-2-sulphopropyl maleate, the alkali salts, ammonium salts, amine salts thereof, and the phosphates described in U.S. Patent 4,101,490, such as dodecyl (hydro~yethyl acrylate) phosphate, polyoxyethylene nonyl phenol (hydro-xypropyl methacrylate) phosphate or lauryl (hydroxyethyl methacrylate) phosphate. The copolymerizable emulsiiiers containing a long polyoxylene chain described elsewhere in the text can also be usad. If the copoly merizable emulsifier has a relatibely low molecular weight, a quantity of batween 0.1 and 1.5 wt.% is preferably used. Ii the molecular weight i9 high due to the presence of a large polyoxyethylene group, the quantity preferably used may also be greater, for instance between 1.0 and 4.0 wt.%o Copolymerizable compounds that contain at least one phos-phoric acid or sulphonic acid group and that can ~unction as emulsion stabilizer are also known. Examples are bis-(2-sulphopropyl) itaconate and the corresponding fumarate and maleate, parasulphophenyl methacry-late and salts thereof, 4-sulphobutyl methacrylate, 2-acrylamido
I-t is known that an aqueous dispersion of a water-insoluble addition polymer, combined with a polymer tha-t is soluble in an aqueous ~lkal ~n~ environ-ment, can be applied as a binder for gloss paint. The coatlng ob-tained is formed substantially by -the insoluble polymer. The polymer that is soluble in an alkal-ine environment ensures good brushability of the system, in particular good flow behaviour, and a good gloss~ and is often used as a grinding aid for the pigment to be included in the paint. A disadvantage of the known systems, described in British Patent speciEication 1,500,517, among others, is that a relatively large quantity of the soluble polymer is required to obtain good brushability, in par-ticular flow. Owing to the presence of comparatively large quantities of alkali-soluble polymer, however, the coating becomes sensitive to moisture penetration, and the alkali resistance and the adhesion to the substrate deteriorate.
The purpose of the invention is an improved aqueous polymer dispersion, in particular a dispersion that can be applied as a binder for gloss paint.
According to one aspect of the present invention there is provided a process for preparing an aqueous dispersion of a water-insoluble polymer compris-ing effecting an addition polymerization of unsaturated monomers in water with an appropriate initiator and at least one emulsifier, wherein the polymeri7.ation mixture comprises between 0.1 and 5.0 wt. % calculated relative to the total quan-tity of monomer of at least one monomer containing a phosphoric acid, sulphonic acid or carboxylic acid group functioning as emulsifier, at least one anionic or non-ionic emulsifier in a quantity of between 0.1 and lO wt. %, calculated rela-tive to the total quantity of monomer, and at least one compound that contains a -33~;
polyoxyethylene chain having between 60 and 400 oxyethylene units and that is chosen from the group consisting oE polyethylene glycols, non-ionic emulsifiers,anionic emulsiEiers and copolymerizable oompounds.
According to another aspect of -the present invention there is provided an aqueous dispersion of a water-insoluble polymer prepared by -the above process.
According to a further aspect of the present invention -there is provi-ded a process for preparing an aqueous polymer dispersion with increased flow, wherein an aqueous dispersion oE a water-insoluble polymer containing between 0.1 and 5.0 wt. %, calculated relative to the total quantity of monomer, of a monomer possessing a phosphoric acid, sl1lphon;c acid or carboxylic acid group Eunctioning as emulsifier, in which dispersion there is at least one compound with a long polyoxyethylene chain containing between 60 and 400 oxyethylene units, chosen from the group of polyethylene glycols, non-copolymerizable non-ionic or anionicemlllq;fiers containing a polyoxye-thylene chain, and copolymerizable compounds containing a polyoxyethylene chain, is mixed with a polymer soluble in an aqueous alkaline medium in a vatio such that -there is between 1 and 25 wt. % alkali-solu-ble polymer present, calculated relative to the total quantity of polymer wherein the alkali-soluble polymer is a copolymer of an acrylate or methacrylate and an unsaturated mono- or dicarboxylic acid unit~
According to a still further aspect of the present invention there is provided a paint comprising a polymer dispersion having increased flow prepared by the above process as a binding agent.
According to another aspect of the present invention there is provided a polymerization mixture as defined above for use in the above process.
According to the invention, an aqueous dispersion of a water-insoluble polymer is prepared by addition polymerization of unsatura-ted monomers in waterwith an appropriate initiator and at least one emulsifier, at least one monomer la ~r~i b, ~
~2~ 335 containing a phosphoric acid, sulphonic acid or carboxylic acid group or a group acting as emulsifier being employed in a quantity of between 0.1 and 5.0 wt. %, calculatecl relative -to the to-tal quantity of monomers, and polymerization being conducted in the presence oE a-t least one non-ionic or anionic emulsifier in a quantity lb ~2~)183S
oi' between 0.1 and 10.0 wt.%, calculated relative to the total quantity oi' monomers, with at least one compound being presen-t that contains a polyoxyethylene chain containing between 60 and 400 oxyethylene units and that is chosen ~rom the group o~ polyethylene glycols, non-ionic or anionio non-copolymerizable emulsiiiers containing a poly-oxyethylene chain and non-lonic or anlonic copolymerizable emulsi~iers containing a polyoxyethylene oha~n.
The invention is based on the iact that at lsast one monomer built into the polymer contains a stabllizine acid group or an emulsi-~ying group and that there is at least one compound with a long poly-oxyethylene chain present. By this combination, dispersions can be obtained that posse3s long shel~ e and good dispersion ~low and good polymer water resistance. These dispersions can in general be applied in coating systems and paints, as additives in construction materials (plaster, cement and concrete mortars), as impregnating agents and adhesives.
The dispersions are especially suitable ~or applications in which a poly~er soluble in an aqueous alkaline environment is also added to the dispersion to improve the ~low. It is ~ound that only a minor quantity o~ alkali-soluble polymer is required to obtain 2 dispersion with good ~low properties. Such mixed systems can be used for the ai'orementioned applications. They are especially suitab}e i'or application as lacquers and as binding agents in gloss paints, more speci~ically air-drying gloss paint~.
The coatings thus obtained have a high gloss, adher~ well, are re-coatable and well resistant to water and alkali. The paints have good brushability due to their excellent i'low.
According to the invention, there should be at least one compound with a long polyoxyethylens chain pre~ent during poly~erization.
This chain should contain between 60 and 400 oxyethylene units. Hence-~orth, a polyoxyethylene group with n oxyethylene units will be indica-ted in complsx compounds by '.nE0', as ior instance in nonyl phenol-.100 E0. The value oi' n is the actual value, determined by analysis.
Polyethylene glycol with a molecular weight of between about 2600 and 15,000 and preferably between 3500 and 6000 can be used as compound with a long polyoxyethylene chain, in a quantity oi between 0.1 and 5.0 wt.%, calculated relative to the quantity o~ monomer. In `~ ~201835 addition to the polyethylene glycol, at least one anionic or non-ionic emulsi-fier should be used. In addition to the polyethylene glycol, an emulsifier with a long polyoxyethylene chain1 optionally copolymerizable, may also be ~Ised.
Application of polyethylene glycol gives good results, but has the disadvantage that an extra, water-soluble co~lponent is added in addition to the emulsifiers.
For this reason, a suitable non-ionic or anionic emulsifier is preferably used as compound with a long polyoxyethylene chain.
Non-ionic or anionic non-copolymerizable emulsifiers with a long poly-oxyethylene chain can be applied separately or in combination in a quantity of between 0.1 and 10 wt. %, preferably between 0.5 and 7.5 wt.%, and in particular between 1.0 and 5.0 wt.%, calculated relative to the quantity of monomer. The polyoxyethylene chain should contain between 60 and 400 oxyethylene units. The best results as regards the brushability, particularly the flow, of the disper-si~ons and lacquers and paints based thereon are achie~ed with chains containing 8Q to 120 oxyethylene units.
Non-ionic emulsifiers with a long polyoxyethylene chain that can potentially be used include a polyoxyethylated C6-C20 alcohol, a polyoxyethylated phenolformaldehyde condensa~e, a polyoxyethylated (C4-C20) alkyl phenol, a poly-oxyethylene-polyoxypropylene block copolymer, or an adduct of ethylene oxide and propylene oxide on a polyamine, which adduct contains one or more polyoxy-ethylene chains. The latter two types of emulsifier should consist to more than 60 wt.% and preferably at least 80 wt.% of polyoxyethylene chain(s). Ex-amples of suitable emulsifiers are nonyl phenol .80 E0, nonyl phenol .100 E0, .200 E0, nonyl phenol .12Q E0, stearyl .100 E0, n-butyl phenol .100 E0~ dodecyl phenol .150 E0, an ethylene oxide/propylene oxide ~80/20) block copolymer with a molecular weight of 8700, an adduct of ethylene oxide and propylene oxide on ethylene diamine consisting to 80 wt.% of oxyethylene units and with a molecular ~Z~ 3S
weight of 8000, and other commercially available products. The above-mentioned types of emulsifier are pre:ferably used in combtnation with a conventional anionlc emuls:ifier containing few or no oxyethylene groups, because polymerization can thus be better controlled.
In general, the sulphonated, phosphated and carboxylated analogues o-f the above-mentioned non-ionic emulsifiers are potential anionic emulsifiers with a long polyoxyctllylene chain, as such or in - 3a -lZ~D18a3S
the ~orm o~ alkali, ammonium or amine salts.
The carboxylate or phosphate product is pre~erablg used, due to the greater improvement o~ the flow behaviour. Examples o~
suitable oompounds are lauryl .l20 E0 phosphate, dodeoyl .100 E0 phos-phate, nonyl .150 E0 carboxylate, nonyl phenol .80 E0 sulphate, nonyl phenol .100 E0 carboxylate, hexyl phenol .120 E0 phosphate and analogou~
compounds.
In addition to the non-copolymerizable emulsiiiers with a long polyoxyethylene chain, other conventional non-ionic or anionic emulsi~iers may also be present that contain ~ew or no oxyethylene units. Examples o~ such non-ionic emulsi~ier3 include nonyl phenol ,20 E0, n-butyl phenol .40 E0, lauryl .25 E0 and ethylene oxide/pro-pylene o~ide block copolymers.
I~ there is a non-ionic 0mulsi~ier with a long polyoxy-ethylene chain present, it is of advantage to apply in addition ananionic emulsifier containing iew or no oxyethylene units. Examples o~ suitable anionic emulsi~iers o~ this type are di-(C6-C12 alkyl) sulphosu¢cinate, dodecyl sulphate, lauryl sulphate, (C4-C20 alkyl) benzene sulphonate, nonyl phenol .10 E0 sulphate, nonyl .5 E0 phosphate, lauryl ,lQ E0 carboxylate, stearyl .~ E0 phosphate and n-o~tyl phos-phate. The total quantity of non-copolymerizable emulsi~ier is 1n all cas0s between 0.1 and 10.0 wt.%, calculated relative to the quantity o~ monomer.
A copolymeri7.able emulsifier can also be used as compound with a long pclyoxyethylene chain, preierably in a quantity o~ between 1.0 and 5.0 wt.%, calculated relative to the total quantity of monomer.
Examples here are nonyl phenol .10~ E0 (hydroxyethyl methacrylate) phosphate, lauryl .120 E0 (hydroxyethyl methacrylate) phosphate, nonyl phenol .80 E0 2-sulphopropyl malea~e, a half-ester o~ maleic acid or ~umaric acid with an ethylene oxide/propylene oxide block copolymer (70 % E0, molecular weight 6500), lauryl .90 E0 2-sulphopropyl itacon-ate, butyl phenol .120 E0 methacrylate, and in general esters o~ a oopolymeri~able acidic compound with one of the non-ionic emulsi~iers with long polyoxyethylene chaine summed up above. These copolymsrizable emulsi~iers, too, should possess a group containing 60-~00 oxyethylene units, and preferably 80-120 oxyethylene units.
In addition to the oopolymerizable emulsiiiers, one or more 12l~ 5 non-copolymerizable emulsifiers can be used.
In the polymerization there should be present between 0.10 Qnd 5.~ wt.%, calculated relative to the total quantity of monomer, of a copolymerizable emulsifier and/Qr a copolymerizable emulsion stabi-lizer po~sesslng a sulphonic acid, phosphorio ac:ld or carboxylic acidgroup. Here, monomers are taken to mean any unsaturated copolymerizable oompounds present. Copolymerizable emulsifiers are known per se.
Examples are dodecyl-2-sulphopropyl itaconate, dodecyl-2-sulphopropyl maleate, the alkali salts, ammonium salts, amine salts thereof, and the phosphates described in U.S. Patent 4,101,490, such as dodecyl (hydro~yethyl acrylate) phosphate, polyoxyethylene nonyl phenol (hydro-xypropyl methacrylate) phosphate or lauryl (hydroxyethyl methacrylate) phosphate. The copolymerizable emulsiiiers containing a long polyoxylene chain described elsewhere in the text can also be usad. If the copoly merizable emulsifier has a relatibely low molecular weight, a quantity of batween 0.1 and 1.5 wt.% is preferably used. Ii the molecular weight i9 high due to the presence of a large polyoxyethylene group, the quantity preferably used may also be greater, for instance between 1.0 and 4.0 wt.%o Copolymerizable compounds that contain at least one phos-phoric acid or sulphonic acid group and that can ~unction as emulsion stabilizer are also known. Examples are bis-(2-sulphopropyl) itaconate and the corresponding fumarate and maleate, parasulphophenyl methacry-late and salts thereof, 4-sulphobutyl methacrylate, 2-acrylamido
2-methylpropane sulphonic acid and salts thereof, and the mono- and diphosphate esters known from U.S. Patent 4,110,285, such as mono-(2-hydroxypropyl methacrylate) phosphate. The stabilizers may possess a free acid group or a salt derlved therefrom. Unsaturated carboxylic acids also exhibit stabilizing activity. ~xamples of stabilizers con-taining a carboxylic group are acrylic acid, methacrylic acid, half-esters of maleic acid, iumaric acid, itaconic acid and citraconic acid such as monobutyl maleate, monoethyl itaconate. To have a stabili-zing effect, these carboxylic acid monomers must be located in the outer skin of the polymer particles. In connection herewith, carboxylic acid monomers intended as StabilizerS should not be added until the end of polymerization. The monomers containing a phosphoric acid or sulphonic acid group may ba added arbitrarily in time and are for this )18~5 reason to be preferred. Monomeric carboxylic acid~ may, however, also be used for other reason~, for example to improve adhesion or for cro3s-linking. Insofar as they are added at the start of polyl~rization or throughout the polymerization, the carboxylic acicls are left out oi consideration ln oalculation of the quantity of copolymerizable emulsion stabilizers. The copolymerizable stabilizers are preferably applied in a quantity of between 0.1 and 1.5 wt.~, calculated reLative to the quantity of monomer. It is slightly more effective to use copoly-meri~able emulsifiers than to build in acidic stabilizers, as regards the combination of emu}sion stability, lacquer or paint ~low and water re.qistance .
The water-insoluble polymer consists substantially of the usual monomers from the group styrene, acrylates, methacrylates, vinyl esters and vinyl chloride. Also such monomers as acrylamide, N-alkoxy-methacryl amide, ~-methyl styrene, acrylonitrile, ethylene, butadiene, unsaturated carboxylic acids, hydroxyalkyl(meth)acrylates, di-ester~
of maleic acid and suchlike may be used. Examples of suitable monomers not yet mentioned are methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate, lauryl acryla~e, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate, glycidyl methacrylate, dibutyl maleate. A small quantity of a poly-functional unsaturated compound can also be applied, such as a di-, tri- or tetra(meth)acrylate or a di- or triallyl compound. Examples here are diethylene glycol diacrylate, trimethylol propane trimethacry-2S late and propylene glycol diallyl ether. A small quantity of a monomeris also preferably applied to increase adhesion to the substrates, such as N-vinyl pyrrolidone~ NN-dimethyl amino-ethanol acrylate, allyl acetoacetate, 2-vinyl pyridine and 4-vinyl pyridine. The weight percen-tage of these special monomers amounts to 0.2 to 5.0 and preierably 0,5 to 1.5, calculated relative to the total quantity of monomer.
In addition to the emulsifier(s), it is advantageous to apply a small quantity of a protective colloid. Suitable types are hydroxyethyl cellulose, polyvinyl alcohol, vinyl pyrrolidone, homo- and copolymers, acrylamide homo- and copolymers, and methacrylic acid homo- and copolymers. Preferably, 0.1 to 1.50 wt.% protective colloid is applied, caloulated relative to the quantity of monomer.
There may also be present in the polymerization mi~ture a quantity of free polyethylene glycol with a molecular weight of between 1000 snd 10,000 in a quantity of at most 25 wt.%, caloulated relative to the quantity oi emulsi~iers containing a long polyoxy-ethylene chain. At higher levels, the coating gloss decreasea pronoun-cedly. Suc~l relatively minor quantities of polyethylene glycol are o~ten present as a contamin~nt in commercially available 0mulsiiiers.
The total quantity~X ~ompounds containing or consisting o~ a long polyoxythylene chain should however not exceed 10 wt.%, calculated relative to the quantity of monomar.
Polymerization is conducted in the usual way, either continu~usly or batchwise. A suitable continuo~s mode o~ operation is described in ~ritish Patent specification 1,220,777. In a bat~hwise mode of operation, all the components may ba added simultaneously, or part of the monomers and,.if so desired~ the emulsifier(s) and initiators may be added in portions during polymeriæation. In general, a dispersion is prepared with a ~olids conte~t of between 30 and 65 wt.%, the mean size o~ the dispersed particles being between 2do and 1500 nm. The pH o~ the dispersion is adjusted after the end o~
polymerization to a value preferably between 7.5 and 9, and most preferably about 8, to incræase the stability. SuitaOla initiators include alkali and amoonium persulphates, organic peroxides and redox system~, ior example those with sodium thiosulphate, sodium metabisulphite or sodium formaldehyde sul~hoxylate as reducing agent.
To increas& the water resistance of the coatings, ammonium sa ts or amine salts ar~ pre~erably used instead o~ alkali salts.
The dispersions of the wat0r-insoluble polymer .obtained according to the invention are pre~erably applied in combina~ion with a polymer soluble in an aqueous alkaline (pH about 8) environ-ment. In general~ between 1 and 25 wt.% of the alkali-soluble polymer may be applied, calculated relative to the total polymer weight. As lit~le as possible solub}e poiymer will preferably be used, becAuse while it is true that this polymer enhances the flow behaviour and the brushability o~ the paint, it decreases the water resistan~e, alkali resistance, adhesion and re-coatability o~ the coa~s. Pre~erably, 3 to 10 wt.% soluble polymer is used. Thæ binding agent system is made by mi~ing a solution o~ ths alkali--soluble ~ 12~ ;3S
polymer into the dispersion prepared according to the invention.
~ very little, i.e. less than about 5 wt.%, al~ali-soluble polymer i9 usedt,it may bs added to the dispersion o~ the insoluble polymer without th~reatening the shel~ e o~ the dispersion. ~he commercially available polymers soluble in an alkali environment and described e.g. in British Patent 1,500,513 and U.S Patent 4,120,841 may be applied. In general, these are copolymers consisting substantially of (meth)acrylates and unsaturated mono- or d~carboxylic acids, ior instance o$ ethyl acrylate or butyl acrylate and (meth)acrylic acid, maleic acid or fumaric acid.
Ii desired, a second polymer dispersion may also be incor-porated in the paint ~ormulation in an amount o~ say up to 25 ~ by weight of the dispersion according to the invention. This may be a conventional polymer dispersion, e.g. based on acrylic and/or methacry-lic esters and/or styrene, serving to lower the price or to in~luencerheological properties oi the paint. The paint ~ormulation may contain ~urther conventional additives such as biocidal agents, anti-foam agents, leveling agents~dispersion aids and the like. High-gloss paints may be prepared by known msthods, e.g by milling the pigment with the water-soluble polymer and adding this dispersion to the poly-mar dispersion obtained according to the invention.
The invention will be elucidated with reference to the following ~l les, without being restricted to the mode of reali-aation described therin.
~xample I
An aqueous dispersion o~ a water-insoluble poly~ r was prepared in a reactor provided with a stirrer, inert-gas ~lusAing system, temperature control and re~lux cooler. In the reactor, 300 parts water were heated to 80 C, a~ter which 19 parts o~ a 10 wt.
aqueous solution o~ ammonium persu~phate was added. Immediately afterward~, metering-in o~ a specially prepared pre-emulsion was started.
The pre-emulsion consisted of:
492 parts water 10 parts methacrylic acid 480 parts butyl acrylate 12a~ 3S
510 parts methyl methacrylate 37 parts nonyl phenol .100 E0 ('long' nonionic emulsi~ier) 8 parts nonyl phenol .5 E0-phosphate (anio~io emulsiiier) 5 parts mono-lauryl-mono(hydroxyethyl methacrylate) pho~pha~e (an emulsl~ier tha~ can be built in, as per U.S. Patent 4,101,490) 2 parts NN dimethyl ethanol amine.
l'he pre-emulsion was added over a period o~ 3.5 hours, the tempera-ture in the reactor being maintained at about 80 C. Aiter this period, the whole sys~tem was allo~ed to continue reacting ~or a ~urther hour at 85 C. The disper~ion waq then cooled to 25 C
and drained o~ through a screen. There was bar01y any coagulation.
A milky white dispersion with a solids cont0nt o~ about 56 wt.% was thus obtained. The pH was adjusted to 8. All parts given in this and the ~ollowing ç~a ~les are parts by weight.
Examples II-X
By th~ method described in Example I, dispersions were prepared~using 480 parts butyl acrylate, 510 parts methyl methacry-late, 10 parts methacrylic acid and 5 parts laur2~-mono(hydroxyethyl-methacrylate) phosphate and Yarious combinations o~ non-copolymeriza-ble emulsi~iers. The quantities and types o~ emulsi$ier applied are given below:
Example I 16 parts sodium lauryl sulphonate 37 parts nonyl phenol .100 E0 Examp}e III 8 parts nonyl phenol .5 E0 phosphate 37 parts nonyl phenol .92 E0 5.5 parts polyethyl~-n~glycol mol. wt. 5000 Example IV 16 parts non~l phenol .5.E0 phosphate 37 parts polyethylene glycol mol. wt. 6000 Example V 37 parts nonyl phenol .120 E0 9 parts lauryl .4 E0 Example VI 8 parts nonyl phanol .5 E0 phosphate 37 parts nonyl phenol .100 E0 mono(hydroxyethyl methacrylate) phosphate, as per U.S.
Patent 4,101,490 Example VII 15 parts nonyl phenol .150 E0 Example VIII 8 parts nonyl phenol .25 E0 sulphate 18.5 parts ethylene oxide~propylene oxide block copo-lymer mol. ~t. 8700, wlth 80 wt.~ E0 (Pluronic~ 68 ex E~SF Wyandotbe) ~J 18.5 parts ethylene oxide/propylene oxlde block copo-ly~er mol, wt. wt. 1500, wlth 50 % E0 (Pluronic ~L 35 ex ~ASF Wyandotte) Example IX 8 parts nonyl phenol25 E0 sulphate 17 parts nonyl phenol .100 E0 20 parts ethylene oxide/propylene oxide block copo-lymer mol. wt. 16,300, ~ith 80 wt.% E0 (PluroniC ~ 108 ex BASF Wyandotte) Example X 8 parts nonyl phsnol.. 5 E0 phosphate 37 parts C12-C13 alkanol .120 E0 Examples XI-XV
By the method described in Example I, dispersions were prepared with other types and/or quantities of monomers and emulsi-~iers. The components applied are given below:
: :
Example XI 480 parts butyl acrylate 500 parts methyl methacrylate 10 parts methacrylic acid 10 parts glycidyl mathacrylate 5 parts lauryl-mono(hydroxyethyl methacrylate) phosphate 8 parts ~onyl phenol .25 E0 sulphate 37 parts nonyl phenol .100 E0 Example XII 560 parts methyl methacrylate 430 parts 2-ethyl hexyl acrylate 10 parts methacrylic aoid 2.5 parts 2-acryloamido-2 methyl propane sulphonic acid 8 parts nonyl phenol ,25 E0 sulphate 37 parts nonyl phenol .120 E0 Example XIII 480 parts butyl aorylate 410 parts methyl methacryl~te -~tr~rk
The water-insoluble polymer consists substantially of the usual monomers from the group styrene, acrylates, methacrylates, vinyl esters and vinyl chloride. Also such monomers as acrylamide, N-alkoxy-methacryl amide, ~-methyl styrene, acrylonitrile, ethylene, butadiene, unsaturated carboxylic acids, hydroxyalkyl(meth)acrylates, di-ester~
of maleic acid and suchlike may be used. Examples of suitable monomers not yet mentioned are methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate, lauryl acryla~e, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate, glycidyl methacrylate, dibutyl maleate. A small quantity of a poly-functional unsaturated compound can also be applied, such as a di-, tri- or tetra(meth)acrylate or a di- or triallyl compound. Examples here are diethylene glycol diacrylate, trimethylol propane trimethacry-2S late and propylene glycol diallyl ether. A small quantity of a monomeris also preferably applied to increase adhesion to the substrates, such as N-vinyl pyrrolidone~ NN-dimethyl amino-ethanol acrylate, allyl acetoacetate, 2-vinyl pyridine and 4-vinyl pyridine. The weight percen-tage of these special monomers amounts to 0.2 to 5.0 and preierably 0,5 to 1.5, calculated relative to the total quantity of monomer.
In addition to the emulsifier(s), it is advantageous to apply a small quantity of a protective colloid. Suitable types are hydroxyethyl cellulose, polyvinyl alcohol, vinyl pyrrolidone, homo- and copolymers, acrylamide homo- and copolymers, and methacrylic acid homo- and copolymers. Preferably, 0.1 to 1.50 wt.% protective colloid is applied, caloulated relative to the quantity of monomer.
There may also be present in the polymerization mi~ture a quantity of free polyethylene glycol with a molecular weight of between 1000 snd 10,000 in a quantity of at most 25 wt.%, caloulated relative to the quantity oi emulsi~iers containing a long polyoxy-ethylene chain. At higher levels, the coating gloss decreasea pronoun-cedly. Suc~l relatively minor quantities of polyethylene glycol are o~ten present as a contamin~nt in commercially available 0mulsiiiers.
The total quantity~X ~ompounds containing or consisting o~ a long polyoxythylene chain should however not exceed 10 wt.%, calculated relative to the quantity of monomar.
Polymerization is conducted in the usual way, either continu~usly or batchwise. A suitable continuo~s mode o~ operation is described in ~ritish Patent specification 1,220,777. In a bat~hwise mode of operation, all the components may ba added simultaneously, or part of the monomers and,.if so desired~ the emulsifier(s) and initiators may be added in portions during polymeriæation. In general, a dispersion is prepared with a ~olids conte~t of between 30 and 65 wt.%, the mean size o~ the dispersed particles being between 2do and 1500 nm. The pH o~ the dispersion is adjusted after the end o~
polymerization to a value preferably between 7.5 and 9, and most preferably about 8, to incræase the stability. SuitaOla initiators include alkali and amoonium persulphates, organic peroxides and redox system~, ior example those with sodium thiosulphate, sodium metabisulphite or sodium formaldehyde sul~hoxylate as reducing agent.
To increas& the water resistance of the coatings, ammonium sa ts or amine salts ar~ pre~erably used instead o~ alkali salts.
The dispersions of the wat0r-insoluble polymer .obtained according to the invention are pre~erably applied in combina~ion with a polymer soluble in an aqueous alkaline (pH about 8) environ-ment. In general~ between 1 and 25 wt.% of the alkali-soluble polymer may be applied, calculated relative to the total polymer weight. As lit~le as possible solub}e poiymer will preferably be used, becAuse while it is true that this polymer enhances the flow behaviour and the brushability o~ the paint, it decreases the water resistan~e, alkali resistance, adhesion and re-coatability o~ the coa~s. Pre~erably, 3 to 10 wt.% soluble polymer is used. Thæ binding agent system is made by mi~ing a solution o~ ths alkali--soluble ~ 12~ ;3S
polymer into the dispersion prepared according to the invention.
~ very little, i.e. less than about 5 wt.%, al~ali-soluble polymer i9 usedt,it may bs added to the dispersion o~ the insoluble polymer without th~reatening the shel~ e o~ the dispersion. ~he commercially available polymers soluble in an alkali environment and described e.g. in British Patent 1,500,513 and U.S Patent 4,120,841 may be applied. In general, these are copolymers consisting substantially of (meth)acrylates and unsaturated mono- or d~carboxylic acids, ior instance o$ ethyl acrylate or butyl acrylate and (meth)acrylic acid, maleic acid or fumaric acid.
Ii desired, a second polymer dispersion may also be incor-porated in the paint ~ormulation in an amount o~ say up to 25 ~ by weight of the dispersion according to the invention. This may be a conventional polymer dispersion, e.g. based on acrylic and/or methacry-lic esters and/or styrene, serving to lower the price or to in~luencerheological properties oi the paint. The paint ~ormulation may contain ~urther conventional additives such as biocidal agents, anti-foam agents, leveling agents~dispersion aids and the like. High-gloss paints may be prepared by known msthods, e.g by milling the pigment with the water-soluble polymer and adding this dispersion to the poly-mar dispersion obtained according to the invention.
The invention will be elucidated with reference to the following ~l les, without being restricted to the mode of reali-aation described therin.
~xample I
An aqueous dispersion o~ a water-insoluble poly~ r was prepared in a reactor provided with a stirrer, inert-gas ~lusAing system, temperature control and re~lux cooler. In the reactor, 300 parts water were heated to 80 C, a~ter which 19 parts o~ a 10 wt.
aqueous solution o~ ammonium persu~phate was added. Immediately afterward~, metering-in o~ a specially prepared pre-emulsion was started.
The pre-emulsion consisted of:
492 parts water 10 parts methacrylic acid 480 parts butyl acrylate 12a~ 3S
510 parts methyl methacrylate 37 parts nonyl phenol .100 E0 ('long' nonionic emulsi~ier) 8 parts nonyl phenol .5 E0-phosphate (anio~io emulsiiier) 5 parts mono-lauryl-mono(hydroxyethyl methacrylate) pho~pha~e (an emulsl~ier tha~ can be built in, as per U.S. Patent 4,101,490) 2 parts NN dimethyl ethanol amine.
l'he pre-emulsion was added over a period o~ 3.5 hours, the tempera-ture in the reactor being maintained at about 80 C. Aiter this period, the whole sys~tem was allo~ed to continue reacting ~or a ~urther hour at 85 C. The disper~ion waq then cooled to 25 C
and drained o~ through a screen. There was bar01y any coagulation.
A milky white dispersion with a solids cont0nt o~ about 56 wt.% was thus obtained. The pH was adjusted to 8. All parts given in this and the ~ollowing ç~a ~les are parts by weight.
Examples II-X
By th~ method described in Example I, dispersions were prepared~using 480 parts butyl acrylate, 510 parts methyl methacry-late, 10 parts methacrylic acid and 5 parts laur2~-mono(hydroxyethyl-methacrylate) phosphate and Yarious combinations o~ non-copolymeriza-ble emulsi~iers. The quantities and types o~ emulsi$ier applied are given below:
Example I 16 parts sodium lauryl sulphonate 37 parts nonyl phenol .100 E0 Examp}e III 8 parts nonyl phenol .5 E0 phosphate 37 parts nonyl phenol .92 E0 5.5 parts polyethyl~-n~glycol mol. wt. 5000 Example IV 16 parts non~l phenol .5.E0 phosphate 37 parts polyethylene glycol mol. wt. 6000 Example V 37 parts nonyl phenol .120 E0 9 parts lauryl .4 E0 Example VI 8 parts nonyl phanol .5 E0 phosphate 37 parts nonyl phenol .100 E0 mono(hydroxyethyl methacrylate) phosphate, as per U.S.
Patent 4,101,490 Example VII 15 parts nonyl phenol .150 E0 Example VIII 8 parts nonyl phenol .25 E0 sulphate 18.5 parts ethylene oxide~propylene oxide block copo-lymer mol. ~t. 8700, wlth 80 wt.~ E0 (Pluronic~ 68 ex E~SF Wyandotbe) ~J 18.5 parts ethylene oxide/propylene oxlde block copo-ly~er mol, wt. wt. 1500, wlth 50 % E0 (Pluronic ~L 35 ex ~ASF Wyandotte) Example IX 8 parts nonyl phenol25 E0 sulphate 17 parts nonyl phenol .100 E0 20 parts ethylene oxide/propylene oxide block copo-lymer mol. wt. 16,300, ~ith 80 wt.% E0 (PluroniC ~ 108 ex BASF Wyandotte) Example X 8 parts nonyl phsnol.. 5 E0 phosphate 37 parts C12-C13 alkanol .120 E0 Examples XI-XV
By the method described in Example I, dispersions were prepared with other types and/or quantities of monomers and emulsi-~iers. The components applied are given below:
: :
Example XI 480 parts butyl acrylate 500 parts methyl methacrylate 10 parts methacrylic acid 10 parts glycidyl mathacrylate 5 parts lauryl-mono(hydroxyethyl methacrylate) phosphate 8 parts ~onyl phenol .25 E0 sulphate 37 parts nonyl phenol .100 E0 Example XII 560 parts methyl methacrylate 430 parts 2-ethyl hexyl acrylate 10 parts methacrylic aoid 2.5 parts 2-acryloamido-2 methyl propane sulphonic acid 8 parts nonyl phenol ,25 E0 sulphate 37 parts nonyl phenol .120 E0 Example XIII 480 parts butyl aorylate 410 parts methyl methacryl~te -~tr~rk
3~
100 parts styren~
10 parts- methacrylic acid 5 parts lauryl-mono(hydroxyethyl methacrylate) phosphate 8 parts nonyl phenol .100 EO
Example XIV 350 parts butyl aorylate 350 parts methyl methacrylate 300 parts butyl mathacrylate 10 parts methacrylic acid 5 parts lauryl-mono~ydroxyethyl mathacrylate) phosphate 37 parts nonyl phenol .100 EO
5 parts protective colloid (Luriskol K 30) Example XV 440 parts butyl acrylate 550 parts methyl methacrylate 10 parts methacrylic acld 2,5:parts lauryl-mono(hydroxyethyl methacrylate) phosphate 10 parts nonyl phenol .25 EO sulphate 35 parts nonyl phenol .100 EO
Comparative examples A en B
By the method described in Example I, dispersions were prepared with the types and quantities oi monomer quoted therein.
Other cmllctfiers w0re, however, used which, contrary to the compo-sitions according to the invention, contained only relatively shortpolyoxyethylene chains. The emulsi~ier combinations were:
Exa~ple A 8 parts nonyl phenol .5 EO phosphate 37 parts nonyl phenol .SO EO
~ le B 8 pa~tQ nonyl phenol .5 EO phosphat0 37 parts ethylene oxide/propylsne oxide bloc~ copo-lymer. mol. wt. 3500, with 50 wt.% EO
(Pluronic P 65 ex BASF Wyandotte).
Preparation and study oi paints Air-drying gloss paints based on tha dispersions obtained according to the invention were prepared in the ~ollowing way.
In a dispersion beaker provided with water-cooling, 22 parts water, 2.5 parts propylene glycol and 6 parts of a dispersion of a poly-mer soluble in an alkaline environ~ent (co~mercial produ~t Viscalex VG 2, Allied Colloids) are mixed. Nex-t, 3 parts 25-% ammonia are added. Owlng to the increased pH, the polymer enters into solution, causing the vi~cosity of the mlxture to increa~e. Then, O.S part3 anti-~oaming agent, 17.5 parts butyl carbitol, 80 parts tltanium dioxide pig~ent and 80 parts glass beads are added. The mixture is ground in a bead ~ or 25 minutes at 2500 revolutions per mlnute. After cooling, the glass beads are screened o$f and the paste stirred into the dlspersion of the water-insoluble polymer.
A-paint ls thus obtained in which there are 12 parts insoluble polymer (calculated as solid matter).to ea~h o~ alkali-soluble polymer. The paint is diluted to measure with water and tested in the ~ollowing manner.
The flow is assessed by applying the paint to glass with a brush. Evaluation runs from 1 (very poor, brush strokes clearly visible) to 5 (excellent, smooth finish under all circumstances).
The gloss is assessed a~ter 7 days, based on the coat applied to the glass.
The re-coatability is assessed by applying to the dry coat another coat 0.075 mm wet thickness with the applicator, allo-wing this to dry for 24 hours~-and evaluating as to the combination of gloss, adhesion and swell.
The water resistance is assessed by applying a layer of -the paint to be tested with a brush to wood grounded with an alkyd resin and allowingthe paint-to~ ~ for~6 hou~s a~ 25C.Drops o$water are thenapplied to the coatand the time is ~easured until blisters are iormed onthe coat.Evaluationruns Yro~l(very poor, blistersafterl hour) to5(excellent, still no blisters a~ter 6 hours). The adhesion of the coattothesubstrate wastheninvestigated.
A number o$ the dispersions obtained according to the foregolng ~Y~ les wera thus applied in paint. The test results are summarized in Table 1.
,.
!
EXAMPLE -~4 ~ty~ gram sheets were made as in Example ~3 uslng unbleached western kra~t pulp and adding polyvinylacetate latexes.
% polyur~t~ane prepolymer amine % Latex PYAc Dry Tensile Wet Tensile Sheet No. salt on pulp on pulp Latex #/1" #/1"
NH432-1 a 0 None 38.5 1.5 NH439-l 0.5 5.0 B 67.6 21.1 -6 2.0 15.0 B 82.2 35.5 -2 0.5 5.0 61 67.7 20.7 -7 2.0 15.0 61 156.5 56.0 B = DARATAK B, a polyvin~lacetate copolymer emulsion 61 = DARATAK 61L, a hig~ molecular weight polyvin~lacetate homopolymer emulsion DARATAK is a registered trademark of W. R. Grace and Co.
EXAMPLE #5 ~ifty gram sheets were made as in Example #3 using unbleached kraft pulp and acry~lic latexes.
: % polyuret~ane prepolymer amine % Latex Acr~lic Dr~ Tensile Wet Tensile 20 ~ 5~0ek No. salt on pulp on pulp Latex#/1" #/1"
NH432-1 0 0 None 38.5 1.5 :NH44Q-1 0.5 5.0 410 36.9 15.5
100 parts styren~
10 parts- methacrylic acid 5 parts lauryl-mono(hydroxyethyl methacrylate) phosphate 8 parts nonyl phenol .100 EO
Example XIV 350 parts butyl aorylate 350 parts methyl methacrylate 300 parts butyl mathacrylate 10 parts methacrylic acid 5 parts lauryl-mono~ydroxyethyl mathacrylate) phosphate 37 parts nonyl phenol .100 EO
5 parts protective colloid (Luriskol K 30) Example XV 440 parts butyl acrylate 550 parts methyl methacrylate 10 parts methacrylic acld 2,5:parts lauryl-mono(hydroxyethyl methacrylate) phosphate 10 parts nonyl phenol .25 EO sulphate 35 parts nonyl phenol .100 EO
Comparative examples A en B
By the method described in Example I, dispersions were prepared with the types and quantities oi monomer quoted therein.
Other cmllctfiers w0re, however, used which, contrary to the compo-sitions according to the invention, contained only relatively shortpolyoxyethylene chains. The emulsi~ier combinations were:
Exa~ple A 8 parts nonyl phenol .5 EO phosphate 37 parts nonyl phenol .SO EO
~ le B 8 pa~tQ nonyl phenol .5 EO phosphat0 37 parts ethylene oxide/propylsne oxide bloc~ copo-lymer. mol. wt. 3500, with 50 wt.% EO
(Pluronic P 65 ex BASF Wyandotte).
Preparation and study oi paints Air-drying gloss paints based on tha dispersions obtained according to the invention were prepared in the ~ollowing way.
In a dispersion beaker provided with water-cooling, 22 parts water, 2.5 parts propylene glycol and 6 parts of a dispersion of a poly-mer soluble in an alkaline environ~ent (co~mercial produ~t Viscalex VG 2, Allied Colloids) are mixed. Nex-t, 3 parts 25-% ammonia are added. Owlng to the increased pH, the polymer enters into solution, causing the vi~cosity of the mlxture to increa~e. Then, O.S part3 anti-~oaming agent, 17.5 parts butyl carbitol, 80 parts tltanium dioxide pig~ent and 80 parts glass beads are added. The mixture is ground in a bead ~ or 25 minutes at 2500 revolutions per mlnute. After cooling, the glass beads are screened o$f and the paste stirred into the dlspersion of the water-insoluble polymer.
A-paint ls thus obtained in which there are 12 parts insoluble polymer (calculated as solid matter).to ea~h o~ alkali-soluble polymer. The paint is diluted to measure with water and tested in the ~ollowing manner.
The flow is assessed by applying the paint to glass with a brush. Evaluation runs from 1 (very poor, brush strokes clearly visible) to 5 (excellent, smooth finish under all circumstances).
The gloss is assessed a~ter 7 days, based on the coat applied to the glass.
The re-coatability is assessed by applying to the dry coat another coat 0.075 mm wet thickness with the applicator, allo-wing this to dry for 24 hours~-and evaluating as to the combination of gloss, adhesion and swell.
The water resistance is assessed by applying a layer of -the paint to be tested with a brush to wood grounded with an alkyd resin and allowingthe paint-to~ ~ for~6 hou~s a~ 25C.Drops o$water are thenapplied to the coatand the time is ~easured until blisters are iormed onthe coat.Evaluationruns Yro~l(very poor, blistersafterl hour) to5(excellent, still no blisters a~ter 6 hours). The adhesion of the coattothesubstrate wastheninvestigated.
A number o$ the dispersions obtained according to the foregolng ~Y~ les wera thus applied in paint. The test results are summarized in Table 1.
,.
!
EXAMPLE -~4 ~ty~ gram sheets were made as in Example ~3 uslng unbleached western kra~t pulp and adding polyvinylacetate latexes.
% polyur~t~ane prepolymer amine % Latex PYAc Dry Tensile Wet Tensile Sheet No. salt on pulp on pulp Latex #/1" #/1"
NH432-1 a 0 None 38.5 1.5 NH439-l 0.5 5.0 B 67.6 21.1 -6 2.0 15.0 B 82.2 35.5 -2 0.5 5.0 61 67.7 20.7 -7 2.0 15.0 61 156.5 56.0 B = DARATAK B, a polyvin~lacetate copolymer emulsion 61 = DARATAK 61L, a hig~ molecular weight polyvin~lacetate homopolymer emulsion DARATAK is a registered trademark of W. R. Grace and Co.
EXAMPLE #5 ~ifty gram sheets were made as in Example #3 using unbleached kraft pulp and acry~lic latexes.
: % polyuret~ane prepolymer amine % Latex Acr~lic Dr~ Tensile Wet Tensile 20 ~ 5~0ek No. salt on pulp on pulp Latex#/1" #/1"
NH432-1 0 0 None 38.5 1.5 :NH44Q-1 0.5 5.0 410 36.9 15.5
-4 2.0 15.0 410 64.0 28.1 NH440-2 0.5 5.0 400 52.8 18.9
-5 2.0 15.0 400 9g.7 53.8 NH440-3 0.5 5.0 442 48.3 16.7
-6 2.0 15.0 442 114.7 54.5 410 a DAREX X410, a vin~l modified acrylic latex 400 = DAREX X400, a self-curing polyacrylic latex 3a 442 = DAREX X442, a st~rene-acr~late copolymer latex DAREX i~ a registered trademark o~ W.R. Grace and Co.
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Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing an aqueous dispersion of a water-insoluble polymer comprising effecting an addition polymerization of unsaturated monomers in water with an appropriate initiator and at least one emulsifier, wherein the polymerization mixture comprises between 0.1 and 5.0 wt. %, calculated relative to the total quantity of monomer of at least one monomer containing a phosphoric acid, sulphonic acid or carboxylic acid group functioning as emulsifier, at least one anionic or non-ionic emulsifier in a quantity of between 0.1 and 10 wt. %, calculated relative to the total quantity of monomer, and at least one compound that contains a polyoxyethylene chain having between 60 and 400 oxyethylene units and that is chosen from the group consisting of polyethylene glycols, non-ionic emulsifiers, anionic emulsifiers and copolymerizable compounds.
2. A process according to claim 1, wherein the polymerization mixture inc-ludes at least one compound with a polyoxyethylene chain containing between 80 and 120 oxyethylene units.
3. A process according to claim 1, wherein the polymerization mixture inc-ludes between 0.5 and 7.5 wt. %, calculated relative to the quantity of monomer, a non-ionic non-copolymerizable emulsifier with a polyoxyethylene chain consist-ing of 60-400 oxyethylene units.
4. A process according to claim 3, wherein the polyoxyethylene chain con-sists of 80-120 oxyethylene units.
5. A process according to claim 3 or 4, wherein the non-ionic emulsifier is chosen from the group consisting of ethoxylated C6-C20 aliphatic alcohols, ethoxylated (C4-C20 alkyl) phenols, adducts of ethylene oxide and propylene oxide on a polyamine, which adducts consist of more than 60 wt. %, of oxyethylene units, and ethylene oxide/propylene oxide block copolymers consisting of more than 60 wt. % of oxyethylene units.
6. A process according to claim 3, wherein the polymerization mixture inc-ludes in addition to the non-ionic emulsifier at least one anionic emulsifier.
7. A process according to claim 1, wherein the polymerization mixture inc-ludes between 0.5 and 7.5 wt. %, calculated relative to the quantity of monomer, an anionic non-copolymerizable emulsifier with a polyoxyethylene chain consisting of 60-400 oxyethylene units.
8. A process according to claim 7, wherein the polyoxyethylene chain con-sists of 80-120 oxyethylene units.
9. A process according to claim 7 or 8, wherein the anionic emulsifier is chosen from the group consisting of phosphated, carboxylated or sulphonated deri-vatives of ethoxylated C6-C20 aliphatic alcohols and ethoxylated (C4-C20 alkyl) phenols, and salts thereof.
10. A process according to claim 7, wherein the polymerization mixture inc-ludes a carboxylate or phosphate.
11. A process according to claim 1, wherein the polymerization mixture inc-ludes a copolymerizable emulsifier with a polyoxyethylene chain consisting of 60-400 oxyethylene units in a quantity of between 0.5 and 5.0 wt. %, calculated relative to the quantity of monomer.
12. A process according to claim 11, wherein the polyoxyethylene chain con-sists of 80-120 oxyethylene units.
13. A process according to claim 1, 2 or 3, wherein the polymerization mix-ture includes between 0.1 and 1.5 wt. % of a copolymerizable monomer containing a phosphoric acid or sulphonic acid group.
14. A process according to claim 1, 2 or 3, wherein the polymerization mix-ture includes additionally between 0.1 and 1.5 wt. % of a copolymerizable emulsi-fier substantially free of any long polyoxyalkylene chain.
15. An aqueous dispersion of a water-insoluble polymer, prepared by a pro-cess according to claim 1, 2 or 3.
16. A process for preparing an aqueous polymer dispersion with increased flow, wherein an aqueous dispersion of a water-insoluble polymer containing bet-ween 0.1 and 5.0 wt. %, calculated relative to the total quantity of monomer, of a monomer possessing a phosphoric acid, sulphonic acid or carboxylic acid group functioning as emulsifier, in which dispersion there is at least one compound with a long polyoxyethylene chain containing between 60 and 400 oxyethylene units, chosen from the group of polyethylene glycols, non-copolymerizable non-ionic or anionic emulsifiers containing a polyoxyethylene chain, and copolymeri-zable compounds containing a polyoxyethylene chain, is mixed with a polymer solu-ble in an aqueous alkaline medium in a ratio such that there is between 1 and 25 wt. % alkali-soluble polymer present, calculated relative to the total quantity of polymer wherein the alkali-soluble polymer is a copolymer of an acrylate or methacrylate and an unsaturated mono- or dicarboxylic acid unit.
17. A process according to claim 16, wherein between 3 and 10 wt. %, calcu-lated relative to the total quantity of polymer, alkali-soluble polymer is emp-loyed.
18. A paint comprising a polymer dispersion prepared according to claim 16 or 17 as a binding agent.
19. A polymerization mixture for effecting an addition polymerization of unsaturated monomers in water with an appropriate initiator and at least one emulsifier, which mixture comprises between 0.1 and 5.0 wt. %, calculated rela-tive to the total quantity of monomer of at least one monomer containing a phos-phoric acid, sulphonic acid or carboxylic acid group functioning as emulsifier, at least one anionic or non-ionic emulsifier in a quantity of between 0.1 and 10 wt. %, calculated relative to the total quantity of monomer, and at least one compound that contains a polyoxyethylene chain having between 60 and 400 oxyeth-ylene units and that is chosen from the group consisting of polyethylene glycols, non-ionic emulsifiers, anionic emulsifiers and copolymerizable compounds.
20. A polymerization mixture according to claim 19, wherein the mixture includes at least one compound with a polyoxyethylene chain containing between 80 and 120 oxyethylene units.
21. A polymerization mixture according to claim 19, wherein the mixture includes between 0.5 and 7.5 wt. %, calculated relative to the quantity of mono-mer, a non-ionic non-copolymerizable emulsifier with a polyoxyethylene chain con-sisting of 60-400 oxyethylene units.
22. A polymerization mixture according to claim 21, wherein the polyoxyeth-ylene chain consists of 80-120 oxyethylene units.
23. A polymerization mixture according to claim 21 or 22, wherein the non-ionic emulsifier is chosen from the group consisting of ethoxylated C6-C20 ali-phatic alcohols, ethoxylated (C4-C20 alkyl) phenols, adducts of ethylene oxide and propylene oxide on a polyamine, which adducts consist of more than 60 wt. %
of oxyethylene units, and ethylene oxide/propylene oxide block copolymers consis-ting of more than 60 wt. % of oxyethylene units.
of oxyethylene units, and ethylene oxide/propylene oxide block copolymers consis-ting of more than 60 wt. % of oxyethylene units.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8001928A NL8001928A (en) | 1980-04-02 | 1980-04-02 | METHOD FOR MAKING POLYMER DISPERSIONS |
| NL8001928 | 1980-04-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1201835A true CA1201835A (en) | 1986-03-11 |
Family
ID=19835099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000374396A Expired CA1201835A (en) | 1980-04-02 | 1981-04-01 | Process for the preparation of polymer dispersions |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4477623A (en) |
| EP (1) | EP0037150B2 (en) |
| JP (1) | JPS56155212A (en) |
| AT (1) | ATE14738T1 (en) |
| AU (1) | AU542047B2 (en) |
| BR (1) | BR8101975A (en) |
| CA (1) | CA1201835A (en) |
| DE (1) | DE3171656D1 (en) |
| ES (1) | ES500847A0 (en) |
| FI (1) | FI68846C (en) |
| MX (1) | MX7264E (en) |
| NL (1) | NL8001928A (en) |
| NO (1) | NO159387C (en) |
| PT (1) | PT72777B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59155413A (en) * | 1983-02-24 | 1984-09-04 | Dainippon Ink & Chem Inc | Resin dispersion and its production |
| US4604414A (en) * | 1983-03-31 | 1986-08-05 | Sumitomo Chemical Company, Limited | Antistatic acrylic resin composition and method for the production thereof |
| DE3402447A1 (en) | 1984-01-25 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | ACRYLATE HYDROSOLE |
| DE3518671A1 (en) * | 1985-05-24 | 1986-11-27 | Basf Ag, 6700 Ludwigshafen | PAINTING WITH AN ADDITION TO A COARSE-PART POLYSTYRENE DISPERSION |
| DE3620679A1 (en) * | 1986-06-20 | 1987-12-23 | Henkel Kgaa | AGENTS FOR TEXTILE EQUIPMENT |
| DE3728992A1 (en) * | 1987-08-29 | 1989-03-09 | Basf Ag | PHOSPHATE GROUPS CONTAINING AQUEOUS DISPERSIONS FOR PAINTING AGENTS |
| US5191029A (en) * | 1988-12-29 | 1993-03-02 | Deldonno Theodore A | Phosphorus-containing polymer compositions containing water-soluble polyvalent metal compounds |
| US5258451A (en) * | 1990-06-07 | 1993-11-02 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of an aqueous emulsion of organopolysiloxane |
| US5191009A (en) * | 1990-09-20 | 1993-03-02 | The Goodyear Tire & Rubber Company | Process for producing stable latex |
| US5663224A (en) * | 1991-12-03 | 1997-09-02 | Rohm And Haas Company | Process for preparing an aqueous dispersion |
| US6080802A (en) * | 1991-12-03 | 2000-06-27 | Rohm And Haas Company | Process for preparing an aqueous dispersion of composite particles including polymeric latex adsorbed to titanium dioxide |
| US5232838A (en) * | 1991-12-09 | 1993-08-03 | Minnesota Mining And Manufacturing Company | Culture media device and method of use |
| DE4141942A1 (en) * | 1991-12-19 | 1993-06-24 | Huels Chemische Werke Ag | METHOD FOR PRODUCING LARGE-PIECE, AQUEOUS PLASTIC DISPERSIONS |
| EP0661302B1 (en) * | 1993-12-23 | 1999-09-01 | Nitto Denko Corporation | Process for producing aqueous Dispersion-Type Acrylic Polymer, the acrylic polymer obtained thereby, and pressure-sensitive adhesive comprising the acrylic polymer |
| US5962580A (en) * | 1995-06-07 | 1999-10-05 | Rohm And Haas Company | Method for providing a waterborne coating composition with improved color acceptance |
| US5731368A (en) * | 1995-09-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Aoueous vinyl polymer dispersions |
| US5782972A (en) * | 1997-03-21 | 1998-07-21 | W.R. Grace & Co.-Conn. | Additive for production of highly workable mortar cement |
| DE69943379D1 (en) | 1998-11-23 | 2011-06-01 | Grace W R & Co | IMPROVED PROCESSING AND LIFE OF MORTAR PLATES FROM MASONAL MORTARS AND METHOD FOR THE PRODUCTION THEREOF |
| DE19939327A1 (en) * | 1999-08-19 | 2001-02-22 | Basf Ag | Binder preparations based on aqueous polymer dispersions |
| KR100401114B1 (en) * | 1999-11-24 | 2003-10-10 | 엄정철 | Water paint composition |
| US6541590B1 (en) | 1999-12-14 | 2003-04-01 | Rohm And Haas Company | Polymeric binders from copolymers of unsaturated carboxylic acids and surfactant monomers |
| US6638998B2 (en) | 2001-04-18 | 2003-10-28 | Basf Ag | Use of surfactants for improving the compatibility of inorganic pigments in aqueous coating compositions |
| DE10332621A1 (en) † | 2003-07-17 | 2005-02-03 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the preparation of polyvinyl alcohol-free, aqueous polymer dispersions |
| US9102848B2 (en) | 2011-02-28 | 2015-08-11 | Basf Se | Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same |
| DE102012019789A1 (en) | 2012-10-09 | 2014-04-10 | Clariant International Limited | Phosphorus-containing polyalkylene glycol block copolymers and their use as emulsifiers for emulsion polymerization |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3202638A (en) * | 1961-06-01 | 1965-08-24 | Shell Oil Co | Freeze-thaw mechanically stable latex of a terpolymer of styrene, alkyl acrylate and an alpha-beta vinylidene carboxylic acid |
| CH425237A (en) * | 1963-12-12 | 1966-11-30 | Ciba Geigy | Process for the emulsion polymerization of unsaturated polymerizable compounds |
| FR1520906A (en) * | 1966-04-02 | 1968-04-12 | Basf Ag | Process for the preparation of suspensions of styrene-butadiene copolymers |
| US3536682A (en) * | 1968-03-04 | 1970-10-27 | Gulf Research Development Co | Self-emulsifiable ethylene polymer compositions |
| US3516975A (en) * | 1968-10-25 | 1970-06-23 | Gen Tire & Rubber Co | Ethylene-vinyl acetate polymers prepared with polyoxyalkylene compounds |
| JPS4932787B2 (en) * | 1971-08-07 | 1974-09-03 | ||
| DE2452585B2 (en) * | 1974-11-06 | 1981-07-30 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of shear-stable aqueous copolymer dispersions |
| DE2604630C2 (en) * | 1976-02-06 | 1982-06-24 | Bayer Ag, 5090 Leverkusen | Process for the production of acrylonitrile-vinyl chloride copolymers with an increased viscosity number |
-
1980
- 1980-04-02 NL NL8001928A patent/NL8001928A/en not_active Application Discontinuation
-
1981
- 1981-03-12 AU AU68298/81A patent/AU542047B2/en not_active Ceased
- 1981-03-25 DE DE8181200330T patent/DE3171656D1/en not_active Expired
- 1981-03-25 EP EP81200330A patent/EP0037150B2/en not_active Expired
- 1981-03-25 AT AT81200330T patent/ATE14738T1/en not_active IP Right Cessation
- 1981-03-30 ES ES500847A patent/ES500847A0/en active Granted
- 1981-03-31 PT PT72777A patent/PT72777B/en not_active IP Right Cessation
- 1981-03-31 NO NO811101A patent/NO159387C/en unknown
- 1981-04-01 FI FI811004A patent/FI68846C/en not_active IP Right Cessation
- 1981-04-01 MX MX819389U patent/MX7264E/en unknown
- 1981-04-01 CA CA000374396A patent/CA1201835A/en not_active Expired
- 1981-04-01 BR BR8101975A patent/BR8101975A/en unknown
- 1981-04-02 JP JP4998881A patent/JPS56155212A/en active Pending
-
1983
- 1983-01-27 US US06/461,493 patent/US4477623A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| MX7264E (en) | 1988-03-11 |
| FI68846C (en) | 1985-11-11 |
| NO159387C (en) | 1988-12-21 |
| EP0037150A3 (en) | 1982-02-17 |
| ES8205423A1 (en) | 1982-06-01 |
| EP0037150A2 (en) | 1981-10-07 |
| AU6829881A (en) | 1981-10-08 |
| FI811004L (en) | 1981-10-03 |
| PT72777A (en) | 1981-04-01 |
| EP0037150B2 (en) | 1989-10-18 |
| ES500847A0 (en) | 1982-06-01 |
| JPS56155212A (en) | 1981-12-01 |
| DE3171656D1 (en) | 1985-09-12 |
| AU542047B2 (en) | 1985-02-07 |
| NL8001928A (en) | 1981-11-02 |
| ATE14738T1 (en) | 1985-08-15 |
| NO159387B (en) | 1988-09-12 |
| US4477623A (en) | 1984-10-16 |
| BR8101975A (en) | 1981-10-06 |
| FI68846B (en) | 1985-07-31 |
| PT72777B (en) | 1982-03-23 |
| EP0037150B1 (en) | 1985-08-07 |
| NO811101L (en) | 1981-10-05 |
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Legal Events
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| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20030311 |